Synthesis of oxygenated compounds



Jan. 29, 1957 f J. T. HARLAN, JR SYNTHESJIS OF OXYGENATED COMPOUNDS 5 Sheets-Sheet l Original Filed Nov. 12, 1946 Nm U mm MV 3 E m n. D. m. a w J w+ ,mw J n Pm. 00

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SYNTHESIS oF OXYGENATED COMPOUNDS Jan. 29, 1957 Original Filed NOV` 12, 1946 3 Shi-f2ebS--Sheel 2 \r\ven1'or2 domesT. Hd an Jr El.) Hm Affor'nel.j w

Jan.. 29, 195? J. T. HARLAN, JR

SYNTHESIS OF OXYGENATED COMPOUNDS Original Filed Nov. 12, 1946 5 Sheets-Sheet 3 (nvenl'r. domea''. Harlan Jr.

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United States Patent O 2,779,802 SYNTHESIS F OXYGENATED COMPOUNDS James' T. Harlan,..lr., Houston,` Tex., assignor `to-Shell Development` Company, Emeryville, Calif., a corporation of Delaware Continuation of abandoned application Serial No. 709,312, November 12,` 1946. This application May` 18, 1953, Serial No. 355,589`

9 iClaims. (Cl'. 2160-638) This invention relates to the production of oxygenated organic compounds through synthesis by a modification ofthe Oxo process. l

The Oxo process provides a means for the synthesis of various oxygenated ,products through the addition of carbon monoxide and hydrogen to compounds containing a suitable linkage. The most important application of the OXO processy is inthe production of carbinols by the additionl-of one molecule of carbon `monoxide and two molecules of hydrogen to compounds containing an unsaturated bond, suchlas an olefin. The` general `reaction of thisprocess may bewritten as follows:

These reactions take place practically-` simultaneously and consequently a complete separation ofthe reactions However, the reaction conditionscom ducive to the first reaction are not optimum fortthe second eaction. Ther process is therefore usually carried out in .p

two steps. Theprimary reaction productisla mixture of the aldehyde and carbinol` and the reactionds completed in thesecond (hydrogenation) step.` The firstor main step of the process is carried ont at altemperaturegbetween aboutSO" C. and 200 C. `andunder a pressure above about 2i) atmospheres in the presenceof aiFischer- Tropsch` catalyst. The reactiomit is seen, iscarried out yunder a considerable partial pressure of carbon monoxide.

Under these conditions a portion of themetal content of thecatalyst is converted to the corresponding metal carbonyl. The metal carbonyl appears to have an important Vinfiuence on the course of therreaction.

ln the usual operation of the process, this metal carbonyl, being soluble in the reaction mixture, is `passed with the reaction mixture from the first step. `Under the strongly hydrogenating conditionsin `thesecond step the metalicarbonyl is decomposed to carbon'monoxide` and This is undesirable since the .carbon monoxide produced poisons the hydrogenating activity of thecatalyst and leads to incompleteconversion. In order to avoid this difficulty ithas been necessary to continuously-,re-

-movescarbon monoxide from the` recycle gas in the -second fsteplby subjecting it to a so-called methanizatiomtreatment followed by considerable bleeding to prevent exces- AThe so-called .methaniza-f 2,779,802 Patented Jan. 29, 1957 In many cases, for instance where the reactants contain sulfur impurities, itis desirable to effect the second step of the process with adifferent, more sulfur-resistantcata# lyst. The presence of metal carbonyl inthe feedto the second stepin this case is also undesirable since it causes a` loss of catalystin the first step and the metal liberated from the carbonylcontaminatesthecatalyst inthe second step.

The process described above is the conventional twostep Oxo processandwill be referred to hereinafter as such.

The process of the invention relates to a modification of the Oxo process, wherein the metal carbonyl inthe reaction product is kdecomposed* and' the liberated carbon monoxide is` removed without consumption or loss of hydrogen. A more particular embodiment of the process Uof the invention relates to the synthesis of carbinols by a modification of the two-step Oxo process, wherein the detrimental effect ofmetal carbonyl in the reaction productin the second step is eliminated and the methanization treatmentmay, be dispensed with. The desired decomposition of the metaly carbonyl and the removal of the liberated carbon monoxide in the reaction vproduct from the first synthesis step are effected according'tothe process of J the invention by first subjecting the reaction product to a change'dsetof conditions of temperature or pressure,v or bothhatwhich the metal carbonyl tends `to decompose andthen'forcing the decomposition to completion underthechanged conditions by physical stripping of the liberated carbon monoxide from the liquid reaction mixture by means. of a substantially inert gas or vapor.

According tor a preferred embodiment of the invention, a normally gaseous hydrocarbompreferably produced as a sideproduct of theprocess, is utilized to eiect decomposition of the metal carbonyl and displace the liberated Ycarbon monoxide-'from the, reaction product of the first `purview of "the invention.

Although the.` moreimportant features which are believed to characterizethe process of the invention have been mentioned above and are particularly pointed out in the claims` appended hereto, the process may be better understoodby referring to the following more detailed description in .which specificillustrations of preferred embodiments are set forth. To assist in this description, reference is had tothe attached drawings wherein there are shown by conventional figures simplified flow diagrams of typical applications of the process of the invention.

In the modifications illustrated in the drawings, a normally gaseous hydrocarbon is utilizedto displace the liberated,carbon'monoxide from` the reaction product of the first step. One suitable application of the processis inthe productionof butyl` alcohol from a refinery socalledpropanefpropylene fraction. Another suitable application of theqprocess is-in the production of amyl alcoholfroma refinery so-called butane-butylene fraction.

-Another suitable application is in the production of nonyl `alcohols from butylene-polymers These applications will propane-propyleaeipfraticn;contamina f-,or example 69% propylene, is introduced via line 1 into line 3 wherein it is commingled with a slurry of the catalyst. A preferred catalyst is cobalt promoted by a minor amount of thorium oxideand supported upon a carrier such as kieselguhr. However, other Fischer-Tropsch type catalysts capable of forming metal carbonyl in the synthesis zone may be employed. Carbon monoxide and hydrogen (synthesis gas) in the proper ratio and amount are introduced to the stream by compressor 6 via lines 7 and 8. Recycle synthesis gas is also introduced into the stream by cornpressor 9 via line 10.

The conditions in reactor S are adjusted and maintained in the known manner to afford substantial synthesis. The reaction temperature may be from about 80 C. to about 200 C. for example, 150 C. The pressure may be from about 20 atmospheres up to several hundred atmospheres, for example 200 atmospheres. Under these conditions the reaction is carried out in the presence of asubstantial liquid phase. The carbon monoxide and hydrogen in the feed to the reactor are preferably present in approximately equal molecular amounts and the total amountis preferably sufficient to agitate the liquid phase and maintain the catalyst in suspension. The amount of catalyst used may vary considerably but may be, for example, about 2%-4% based on the liquid phase. The residence time of the liquid in the reactor may vary depending upon tlie temperature, pressure, and activity of the catalyst, but is usually in the order of 10 minutes. The

reaction is exothermic and some cooling is usually necessary to maintain the chosen temperature. This may be effected by cooling coils in the reactor (not shown).

For the purpose of obtaining a more complete reaction, the reaction mixture from reactor is preferably, but not necessarily, passed to a second stage reactor operated at a somewhat higher temperature (for instance, 30 C. higher) than the first reactor. Thus, in the modification illustrated, the reaction product from reactor 5 is passed via lines 12 and 13 to reactor 11. The necessary heat may be supplied by heat exchanger 14. Additional synthesis gas approximately equivalent to the amount consumed in reactor 5 is introduced via lines 7 and 13.

The reaction mixture from reactor 11 is cooled somewhat and passed to a high pressure separator 15. Unreacted synthesis gas is passed via line 17 to line 10 and recycled. The liquid product from separator 15 is passed to a low temperature separator 18. Here, due to the drop in pressure, a considerable part of the propane is separated. This propane, it will be appreciated, is derived from side reactions (hydrogenation of propylene) as well as from the propane-propylene feed. The vaporization of the propane exerts a considerable cooling effect. Consequently, the temperature in separator 18 is below that in separator 15. The vapor phase product from separator 18, consisting of propane with minor amounts of aldehyde, alcohol and synthesis gas, is further cooled and passed to separator 16 to separate substantially all of the aldehyde and alcohol. The separated fraction is passed via line 19 and combined with the main reaction product in line 20. The uncondensed vapors from separatorld, now consisting essentially of propane and synthesis gas, may be withdrawn from the system via line 21, or they may be compressed and recooled to separate propane. In this latter case the separated synthesis gas is recycled via line and the propane is withdrawn via line 22. In some cases it may be desirable to recombine some of the separated propane with the main reaction product. This may be done by means of bypass line 23.

The liquid product from separator 18 contains the catalyst in suspension and also contains dissolved carbon monoxide and dissolved metal carbonyl. For example, it may contain about 0.5 gram of cobalt as cobalt carbonyl per liter. In the absence of an appreciable partial pressure of carbon monoxide, the metal carbonyls are unstable and decompose at fairly low temperature. Cobalt carbonyl, for example, has a decomposition temperature of about 60 C. When under a high partial pressure of carbon monoxide, however, as in the first reaction zone, the metal carbonyl is stable up to considerably higher temperatures. For example, cobalt carbonyl is stable up to a temperature of about 130 C. when under a partial pressure of carbon monoxide of about atmospheres. By merely reducing the pressure on the reaction product from the first step while maintaining the temperature above the decomposition temperature, the metal carbonyl is therefore caused to decompose. Merely reducing the total pressure is not sufficient, however, to cause the decomposition to proceed to completion at a sufiiciently fast rate. In the process of the invention the rate of decomposition and the completeness of decomposition are improved by the described stripping or displacement action of the inert gas or vapor. This gas or vapor physically removes dissolved carbon monoxide according to the known laws. In the process of the invention the magnitude of the reduction in pressure is not critical since the stripping by the gas is effective in reducing the partial pressure of carbon monoxide in contact with the dissolved metal carbonyl. However, some reduction in pressure is desirable, and reduction to substantially atmospheric pressure, for instance, 1 to 3 atmospheres absolute, is preferred.

In accordance with the above explanations, the liquid product from separator 18 is passed via line 20 to displacement column 24 wherein the substantially complete decomposition of the metal carbonyl is effected. The temperature may be adjusted through control of the temperature of the materials charged. This may be accomplished by means of heat exchangers 25 and 26 and/or by means of external recirculation through heating coils (not shown). Typical conditions are, for example, a temperature between about 70 C. and 100 C. and substantially atmospheric pressure.

Displacement column 24 may be simply a long tubular column provided with a gas distributing plate near the bottom. It may be improved in efficiency however, by the proper use of baiiies or vertical partitions dividing the column into a number of long narrow cells. Such modifications are well known to those skilled with the design of strippers and are not illustrated in the drawing.

As pointed out above, the gas utilized to displace or strip the liberated and dissolved carbon monoxide from the reaction mixture in this modification is propane. Thus, propane substantially free of carbon monoxide is introduced into displacement column 24 near the bottom via line 48.

The liquid product from displacement column 24 con tans the catalyst in suspension as wel] as the suspended metal produced by decomposition of the metal carbonyl. In many cases it may be desired to pass this product directly to the second step of the process. However, the suspended catalyst is only a fair hydrogenation catalyst and is furthermore quite sensitive to poisoning by sulfur compounds. It is therefore desirable to employ a more active and less sulfur-sensitive catalyst in the last step. This is accomplished in this modification as follows:

The liquid product from the displacement column 24 is passed to a filter 28 via line 29. The filtrate substantially free of catalyst is then passed via line 30, pump 31, heater 32 and line 33 to a reactor 34. Hydrogen substantially free of carbon monoxide is introduced via pump 35 and line 36.

Reactor 34 is operated to provide the straightforward and simple hydrogenation of butyraldehyde. This may be effected with any one of a large number of known hydrogenation catalysts such as nickel sulfide, tungsten sulfide, copper chromite, and nickel. Merely by way of example one suitable set of conditions is to use a conventional supported nickel hydrogenation catalyst at a temperature of about 175 C. and at a pressure of about p. vs. i. g.

The reaction product is cooled and passed to separator 37. Unused hydrogen isrrecycled vial line 38. TheI liquid reaction product is then passedto a1fractionator39 which isoperated to separate propane from thehigher boiling reaction products. Thisr-propaneis passed to: the displace` ment column as previously mentioned. The depropanized product is then `passed to a fractionating` column 40 which is operated to `separategthe butyl alcohol from higher;` boilingzside reaction products. Thealcoholis removed via line. d and the` higher bolingresidue is removed via line 3. This higher boilingrresidue is utilized to introduce the 4catalyst into reactor' as a-slurry. rIhus, part of it may be passedrbyiline rdzntoxmixing tank 2. Fresh catalyst is introduced'via line 4,3. The-partially spent `catalyst separated fromme.` reaction `product bytilter 28 is usually partially Withdrawn via` line 44 and theyremainder passed to mixing tank 2. lby line 45 and,` hence, recycled. If desired, part ofthereaction product may be passedtothe mixing tank via` line d6 tothin out the; slurry.

The modificationillustrated in Figure II differs from that illustrated in Figure I principally in that asingle catalyst is used and the `heavy fraction of the product is used to recover aldehyde and alcoholwfrom the effluent by-product streams. Inthe modification illustrated in Figure II, the first `step of the synthesis is carried out as described in connectionwithFigure Irexcept that `a refinery butane-butylene fraction-isused in place of the propane-propylene fraction.` The product after-,separating the recycle gas is passed tothe low pressure separator 51. Here butane containing some metal carbonyl and some dissolved gas is separated. The liquid reaction product is then passed to the displacement column 52 wherein itis subjected toa stream of hotbutane injected via line 53 while beingheld at a temperature which is above decomposition temperatureof the metal carbonyl. The liquidproduct,` now free of carbon. monoxide and metal carbonyl and containing thecatalyst in suspension, is passed via line 54 to hydrogenationreactor 55. The conditions in reactor 55` may be, for example, 190 atmos-` pheres and 200 C. Hydrogenis suppliedvia line 59. The total reaction Yproduct is passed` via line 56.to separator '7. Unreacted hydrogen is withdrawn via line 53, and recycled. `The liquid productis then passedrvia line 60 to a settler 61. In settler 61 the bulk of the catalyst lcollects at the bottom and is withdrawn as a slurry via line 62 and recycled to the first stage of the synthesis. The liquid product still containing a small amount of suspended catalyst is withdrawn near the top via4 line163 and passed to filter 64. Partially spent catalyst is withdrawn via line 65. The clarified liquid product is then passed to arseriesof two fractionating` columns 66-and 67. In the first the butane is separated and removed overhead. This butane is cycled to the displacement column wherein it is used to decompose the metal carbonyl. Inthe second fractionating column thealcohol product, in this case amyl alcohol, is separated and removed overhead via line 68. The higher boiling residueis passed via line 69 to an absorber 70. Any excess beyond that requiredffor this purpose may be withdrawn via line `71.

The vaporous products from separator 51 and displacement column 52 are passed to absorber 70 via lines 72 and 73, respectively. These vapors normally contain small to appreciable amounts of alcohol and aldehyde and usually also some metal carbonyl. By contacting these vapors with the higher boiling residue in absorber '70, these valuable products are recovered. Theabsorber liquid containing the absorbed. aldehyde` and` alcohol ,and some of the butane is withdrawn from absorber 70 via line 75 and combined with the reaction product passing to displacement column 52. The excess butane is withdrawn With the carbon monoxide via line '74.

Figure III illustrates a further embodiment of the process of the invention which includes additional novel and advantageous features. In this modification, the Oxo process is in novel combination with the production of synthesis gas. The feeds to the plant are air, natural gasand olefin. Themodification illustrated in this figure willbe described in connection with Hthe y.synthesis 4of high boiling alcohols usingy ahighfboilingplensuch as` a polymer consisting largely of diisobutylene and triisobutylene. Theolen entering via line 4101is first utilized to scrub thel exity gasesfromthe first stageof the synthesis to recover product values therefrom. Thus the4 olefin 4feed is contacted withrrecycle gas from the first synthesis stage in scrubber v102. The scrubbed gas is discharged byline 103 andthe olefin containingrecovered material is thenpassed by line 104 to mixing tank 105 wherein it is slurried with the catalyst. The olefin containingithe catalyst in suspension is passed tothe first synthesis stage byline 106. Recycle synthesis gasis introduced by line .107. Fresh synthesis gas is introduced by line 108. The first synthesis stage is carried out in a manner analogous to that described in connection with the other figures. ,Recycle lgasY from thefirst synthesis stage isseparated from the bulk ofthereaction product in separators 109land .1,10 and passed via line 111 to recycle line 107. A part of thelgas is withdrawn by line `1 12 and, passed to scrubber 102.

The liquid reaction product containing dissolved carbon. monoxide' and metal carbonyly and containing catalyst insuspensionis` passed-.byline H3 to the displacement column llliwherein decomposition of the metal carbonyl is effected and the carbonrnonoxide is stripped as previously described. In this modification this is effected `using naturalgas. Thusnatural gas for the plant entersvia line'114', and'is passed to the distributor of the displacement column by-linel15. The natural gas containing carbon monoxide and some product values is withdrawn from the displacement column by line H6. After recovering product values in separatorl 117 the natural gasy containing `carbon monoxide ispassed by lineilifi to the synthesisrgasproduction step. Air is first separated into oxygen and nitrogen vin. aconventional air reduction step. The oxygen is thenreacted with the natural gas to pro duce synthesis gas. The synthesis gas normally contains hydrogen and carbon monoxide in a ratio of about 2:1. Whilethis is about thecorrect ratio theoretically required for synthesis of carbinols,.it is not the optimum ratio for use-in the `first stage of the synthesis. The synthesis gas is therefore separated into a hydrogen fraction and a fraction containing the carbon monoxide in `a gas separation step. The separation maybe effected` through lthe so-called Water gas shift reaction or in any other desired manner. The hydrogen is passed by line` H9 to the sec ond synthesis stage which is carried out as described in connection with Figure I. The carbon. monoxide fraction of the synthesis gas is passed by line idd to the first synthesis stage. Hydrogen to provide the desired ratio of hydrogen to carbon monoxide in the first synthesis stage is provided by withdrawing the necessary amount of re cycle gas from the second synthesis stage and passing it to the first synthesis stage.` Line is provided for this purpose.

The most important technical application of the process of `the invention is in the production of saturated primary alcohols from aliphatic olefins having between 2 and about 2O carbon atoms. In this application any of the aliphatic olefins may be used. Thus the olefin may be a primary, secondary or tertiary olefin or mixture thereof. The olefin does not necessarily have to be pure but may contain small amounts of sulfur compounds, nitrogen compounds or other normal impurities. Also inert diluent materials such as `aromatic or saturated hydrocarbons, alcohols, ketones, organic acids, ethers and steam may be present. Very suitable sources of olefins are the various olefin polymer fractions obtained by the polymeriza tion of lower olens and olefinic products of cracking, dehydrogenation and related processes.

An important application of the process is the production of higher alcohols (for instance having from about 9 to about 17 carbon atoms) as intermediates in the production of detergents and related products. For this purpose alcohols having relatively straight chains are preferred. Since the oleiins produced by the cracking of petroleum wax and those produced by the polymerization of ethylene are predominantly straight chain oleiins, these oletinic products are particularly suitable feeds.

While the process is at present primarily of importance for the production of open chain monohydric alcohols, the process is .also applicable for the produc-tion of carbinols having aromatic and cycloparaiiin groups, as by the application of such oletinic materials as cyclohexene, cyclopentene, cyclohexylethylene, styrene and the like. Also it may be applied for the production of polyhydric carbinols from materials containing two or more ethylenic bonds such as butadiene, cyclohexadiene, etc. Hydrocarbons having one or more .acetylenic linkages may also be applied.

While unsaturated hydrocarbons are by far the cheap est raw materials and are of primary interest, .at present the process is not limited to the use of these materials. Thus, various oxygenated compounds containing an unsaturated bond such as unsaturated aldehydes, ketones, acids, esters, alcohols and ethers may be employed. Carbon monoxide and hydrogen add to the unsaturated bond in such compounds in a similar manner. Thus, from an unsaturated aldehyde or alcohol a saturated dihydric alcohol is produced, and from unsaturated ketones, acids, esters and ethers the corresponding carbinol addition products are formed.

This application is a continuation of application Serial Number 709,312, led November 12, 1946, now abandoned, which application is a continuation-in-part of application Serial Number 689,377, tiled August 9, 1946, now abandoned.

I claim as my invention:

1. In the synthesis of a carbinol having from about 9 to about 17 carbon atoms by the two-step Oxo process, the improvement which comprises passing a substantially inert vapor up through the liquid intermediate aldehydic reaction product containing dissolved cobalt while maintaining said reaction product at a temperature below the synthesis temperature but above 60 C. for a time to produce a reaction product substantially free of dissolved cobalt and carbon monoxide formed upon decomposition of the soluble cobalt compounds.

2. In the synthesis of an oxygenated compound having from about 9 to about 17 carbon atoms by the two-step Oxo process, the improvement which comprises passing vapors of methane up through the liquid intermediate aldehydic reaction product containing dissolved cobalt while maintaining said reaction product at a temperature below the synthesis temperature but between about 70 C. and 100 C. for a time to produce a reaction product substantially free of dissolved cobalt and carobn monoxide formed upon decomposition of the dissolved cobalt compounds and reacting the methane after passing up through said reaction product with oxygen to form synthesis gas used in said Oxo process.

3. In the production of a carbinol having from about 9 to about 17 carbon atoms by the two-step Oxo process, the improvement which comprises stripping thereaction product of the first step containing dissolved cobalt of carbon monoxide prior to subjecting it to the second step by bubbling therethrough vapors of a saturated hydrocarbon by-product of `the process while maintaining said reaction product at a temperature below the synthesis temperature but between about 70 C. and 100 C. and

at a pressure below the reaction pressure in the first step.

4. In the production of a carbinol having from about 9 to about 17 carbon atoms by the two-step Oxo process, the improvement which comprises stripping the reaction product of the rst step containing dissolved cobalt of carbon monoxide prior to subjecting it to the second step by bubbling therethrough a substantially inert vapor while maintaining said reaction product at a temperature below the synthesis temperature but between about C. and C. and at a pressure below the reaction pressure in the first step, thereby to eiiect substantially complete decomposition of the soluble cobalt compounds.

5. In the production of a carbinol having from about 7 to about 17 carbon atoms by the two-step Oxo process, the improvement which comprises stripping the reaction product of the iirst step containing dissolved cobalt of carbon monoxide prior to subjecting it to the second step by bubbling therethrough a substantially inert vapor while maintaining said reaction product at a temperature below the synthesis temperature but between about 70 C and 100 C. and at substantially atmospheric pressure, for a time sufficient to eiiect substantially complete `decomposition of the soluble cobalt compounds thereby to free the said reaction product of said dissolved cobalt.

6. In the synthesis of an alcohol having from about 9 to about 17 carbon atoms by the twostep OXo process, the improvement which comprises cooling the liquid aldehydic reaction product of the first synthesis step to a temperature below the synthesis temperature in said rst step but above 70 C., passing the cooled reaction product downwardly countercurrent to an ascending stream of substantially inert gas under a pressure below the synthesis pressure in said first step, thereby to effect substantially complete decomposition of dissolved cobalt compounds to metallic cobalt, and separately recovering vaporized reaction product from said substantially inert gas.

7. In the synthesis reaction for the preparation of oxygenated compounds wherein olens, carbon monoxide and hydrogen are reacted in the presence of a cobalt catalyst under conditions which produce oxygenated synthesis products contaminated with dissolved cobalt carbonyl, the method of freeing the synthesis products of such cobalt carbonyl which comprises, treating said contaminated synthesis products, under non-reducing conditions and under conditions causing decomposition of cobalt carbonyl accompanied by consequent liberation of carbon monoxide, with an inert gas to remove carbon monoxide therefrom, and removing the effluent gases.

8. ln the process of removing dissolved cobalt carbonyl from the liquid oxygenated product of the conversion of organic compounds having an olelinic double bond with CO and H2 in the presence of carbonyl-forming cobalt catalysts, said liquid oxygenated product comprising substantial amounts of aldehydes, by heating said liquid product in a catalyst decomposition zone under catalyst decomposition conditions including elevated temperatures, the improvement which comprises maintaining ldecomposition temperature by mixing said product in said catalyst decomposition zone with a fluid suicieut in amount and preheated in the absence of dissolved cobalt carbonyl to a temperature sufficient to keep the mixture formed at said decomposition temperature.

9. The process of claim 8 in which said fluid is a gas.

References Cited in the tile of this patent UNITED STATES PATENTS 2,596,920 Smith et al. May 13, 1952 

8. IN THE PROCESS OF REMOVING DISSOLVED COBALT CARBONYL FROM THE LIQUID OXYGENATED PRODUCT OF THE CONVERSION OF ORGANIC COMPOUNDS HAVING AN OLEFINIC DOUBLE BOND WITH CO AND H2 IN THE PRESENCE OF CARBONYL-FORMING COBALT CATALYST, SAID LIQUID OXYGENATED PRODUCT COMPRISING SUBSTANTIALLY AMOUNTS OF ALDEHYDES, BY HEATING SAID LIQUD PRODUCT IN A CATALYST DECOMPOSITION ZONE UNDER CATALYST DECOMPOSITION CONDITIONS INCLUDING ELEVATED TEMPERATURES, THE IMPROVEMENT WHICH COMPRISES MAINTAINING DECOMPOSITION TEMPERATURE BY MIXING SAID PRODUCT IN SAID CATALYST DECOMPOSITION ZONE WITH A FLUID SUFFICIENT IN AMOUNT AND PREHEATED IN THE ABSENCE OF DISSOLVED COBALT CARBONYL TO A TEMPERATURE SUFFICIENT TO KEEP THE MIXTURE FORMED AT SAID DECOMPOSITION TEMPERATURE. 